Clean flame retardant compositions with carbon nano tube for enhancing mechanical properties for insulation of wire and cable

ABSTRACT

Commercial thermoplastic clean flame retardant materials in wire and cable insulation are mechanically unstable due to high filler loading. In the present invention, thermoplastic, black color, clean flame retardant composition using carbon nano tubes (CNT) is made. The resultant compositions possess very low smoke and toxicity. CNT with outer diameter of 40-60 nm and length of under 20 μm are used to increase mechanical properties and flame retardancy. Thermo plastically extruded composition consists of each component by parts by weight as follows: 100 of resin (polyolefin or 100 of polyolefin/ethylene propylene diene monomer (EPDM)), 90-150 of non-halogen containing flame retardants, 1-20 of auxiliary secondary flame retardant agents, 2-4 of CNT (outer diameter of 40-60 nm) and length under 20 μm and 0.2-1.0 of antioxidants. A reliable method for producing thermoplastic black color clean flame retardant insulation material for wire and cable without deterioration of mechanical properties is discussed.

CLAIM OF PRIORITY

This application is a divisional application and claims priority of U.S.patent application Ser. No. 12/684,139 titled CLEAN FLAME RETARDANTCOMPOSITIONS WITH CARBON NANO TUBE FOR ENCHANCING MECHANICAL PROPERTIESFOR INSULATION OF WIRE AND CABLE filed on Jan. 8, 2010.

FIELD OF INVENTION

This disclosure generally relates to non-toxic, halogen freethermoplastic flame retardant composition containing carbon nano tube(CNT) as insulating material for wire and cable. More particularly, thisinvention relates to clean flame retardant compositions for increasingflame retardancy without deterioration of mechanical properties.

BACKGROUND

Every year, the world faces huge losses in lives and property due toresidential and commercial fires caused by, electrical wiring. Humanlives can be lost due to high temperature flames, toxic smoke and gasthat are generated from the flammable insulation materials used in wireand cable during fire.

The current population uses many equipment and gadgets that containseveral wires and cables. Most wires and cables are fabricated fromplastic materials that are readily flammable. Moreover, modern livinginvolves heavy use of electric equipment containing wires andcommunication systems made of cables. These conditions further increasethe loss of lives and properties due to bad insulation of a wire or acable resulting in an electrical fire. Smoke and toxic fumes from poorinsulation materials in wires and cables can cause irreparable healthdamage.

Wire and cable insulations are required to meet not only the electricalproperties but also the mechanical properties. Polyethylene andpolyvinylchloride compounds are some of the best materials suitable forwire and cable insulations because of their excellent electrical andmechanical properties. However, these materials have poor flameretardancy and generate toxic gases during a fire.

Polyethylene, for example, is easily flammable and generates less toxicgases during the burning process. On the other hand, Polyvinylchloridecompounds generate a lot of toxic gases during a fire, even though ithas acceptable flame retardancy. Currently, clean flame retardantmaterials are made from special formulations. These special formulationsare made of halogen and toxicity free chemicals. Clean flame retardantmaterials mainly consist of matrix polymers that do not contain halogen,main flame retardants, secondary flame retardants, intumescent flameretardants, processing aids and antioxidants. (Mans V et al. 1998, Rai Met al. 1998, Wei P et al. 2006 and Luciana R et al. 2005). The resultantmixture has very poor mechanical properties.

The other biggest problem with commercially clean material is that theyhave unstable mechanical properties, even though they possess high flameretardancy, due to high filler loadings. Clean flame retardant materialscontain relatively high content of inorganic materials as flameretardants. In general, high levels of flame retardants are necessary toachieve commercially acceptable flame retardancy levels for wires andcables. However, high levels of flame retardants may lead todeterioration of mechanical properties. Insulation and jacket materialsfor wire and cable should meet appropriate standards for tensilestrength, elongation at break, thermal resistance and flame retardancyfor an extended application time. Enhanced cable insulations must alsomeet IEC 60502, BS 6724 and BS 7655 standards specific for thermoplasticcompound requirements.

EVA(ethylene vinyl acetate), EVA/LDPE (low density polyethylene) (orLLDPE (linear LDPE), ethylene alpha olefin or ethylene ethyl acrylateare widely used as matrix polymer because of their high flame retardantload ability and increased flame retardancy. Main flame retardantsmostly comprise of inorganic materials, such as, aluminum trihydroixide(ATH), magnesium hydroxide (MH) and huntite hydromagnesite (HH). Theyexhibit high decomposition temperature and have the ability to suppresssmoke as clean flame retardant materials. However, more than 50% w/wloading is required to achieve the target flame retardancy.Unfortunately, such high contents of flame retardants can lead tointerfacial problems between matrix polymer and flame retardants andthen, can negatively affect the mechanical properties.

Various studies were performed to improve mechanical properties andflame retardancy by using organic encapsulated flame retardants (Changet al. 2006, Du L et al. 2006, Liu Y et al. 2006), and synergisticeffect of hydrotalcite with two flame retardants and organo-modifiedmontmorillonite (Laoutid F et al. 2006, Ma H et al. 2006).

Organic encapsulated flame retardants can enhance the interfacialadhesion with matrix polymers and lead to improved dispersion comparedto non-encapsulated flame retardants. Hydrotalcite composites increaseflame retardancy by releasing more gas compared to other flameretardants during burning. In addition, partial substitution of flameretardants by organo-modified montmorillonite improves the burningproperties. All these result only in improved flame retardancy.

Specification standards for wire and cable insulation compositionrequire high flame retardancy and superior mechanical properties. Forexample, the minimum required tensile strength is 8.8 MPa and minimumelongation at break is 125% based on IEC 60502, BS 6724 and BS 7655standards for thermoplastic compounds. Moreover, additional treatment offlame retardants or mixing with special chemicals increase costperformance of final products. There is a need to obtain a wire andcable insulation material that contains a clean flame retardantmaterial, has superior mechanical properties and high flame retardancy.Without meeting these important properties, the clean flame retardantmaterials are not suitable for wire and cable insulation purposes.

SUMMARY

The current invention is carried out to find a flame retardant materialwhich does not generate toxic gases for wire and cable insulationmaterials during a fire. The flame retardant materials are known ashalogen free flame retardant compounds (HFFR compounds), clean flameretardant materials and/or non-toxic flame retardant materials.

The current invention relates to thermoplastic (not thermosetting) typeclean flame retardant materials for wire and cable. The currentinvention pertains to unique formulations and processing methods ofclean flame retardant materials of wire and cable. Partiallycrosslinkable clean flame retardant compositions, which can be partiallycrosslinked by routine thermoplastic extruder without using post curingsystems, are described. The current invention of clean flame retardantcompositions are particularly suitable for use in enhanced cableinsulations to meet the requirement of thermoplastic compound standards.

In general, polymer parts in clean flame retardant compositions areunder 50% by weight and flame retardants parts are over 50% by weight.Moreover, the particle size of most flame retardants used in clean flameretardant materials is under 50 μm, which enables excellent dispersionof polymer/flame retardants/Carbon Nano Tube (CNT) in the composition.Therefore, at first, three different types of multi-walled CNT withdifferent diameter range for e.g. 10-15 nm, 40-60 nm and 60-80 nm areinvestigated to establish better compatibility with the other materialsin thermoplastic clean flame retardant compositions. It was found thatCNT with outer diameter of 40-60 nm and length distribution under 20 μmmay show improved results in terms of mechanical properties and flameretardancy. Hence, CNT can be used in thermoplastic clean flameretardant compositions instead of carbon black to improve mechanicalproperties and flame retardancy.

The instant composition is processed by routine thermoplastic extruderand may show improved mechanical properties and flame retardancy.Composition mainly comprises of 100 parts by weight of resin (polyolefinor 100 parts by weight of polyolefin/ethylene propylene diene monomer(EPDM)), 90-150 parts by weight of non-halogen content main flameretardants, 1-20 parts by weight of auxiliary secondary flame retardantagents, 2-4 parts by weight with CNT of outer diameter of 40-60 nm andlength distribution of under 20 μm and 0.2-1.0 parts by weight ofantioxidants. The present invention demonstrates a reliable method ofproducing black color clean flame retardant insulation material forwires and cables. The said composition also possesses a high flameretardancy and meets the specification standard for mechanicalproperties as an insulation material for wires and cables.

BRIEF DESCRIPTION OF THE FIGURES

Example embodiments are illustrated by way of example and not limitationin the figures of accompanying drawings.

FIG. 1 illustrates EDAX micrographs of CNTs that are taken by EDAXsystem, Model NNL200 from FEI Company, Netherlands.

FIG. 2 illustrates elongation at break of ethylene vinyl acetate(Evaflex 360)/120phr magnesium hydroxide (MAGNIFIN A Grades H10A)formulations as a function of CNT or carbon black content.

FIG. 3 illustrates tensile strength of ethylene vinyl acetate (Evaflex360)/120phr magnesium hydroxide (MAGNIFIN A Grades H10A) formulations asa function of CNT or carbon black content.

FIG. 4 illustrates LOI (%) of ethylene vinyl acetate (Evaflex360)/120phr magnesium hydroxide (MAGNIFIN A Grades H10A) formulations asa function of CNT or carbon black content.

FIG. 5 illustrates elongation at break of ethylene vinyl acetate(Evaflex 360)/linear low density polyethylene (LLDPE 118W)/120phrmagnesium hydroxide (MAGNIFIN A Grades H10A) formulations as a functionof CNT 50 or carbon black content.

FIG. 6 illustrates tensile strength of ethylene vinyl acetate (Evaflex360)/linear low density polyethylene (LLDPE 118W)/120phr magnesiumhydroxide (MAGNIFIN A Grades H10A) formulations as a function of CNT 50or carbon black content.

FIG. 7 illustrates LOI of ethylene vinyl acetate (Evaflex 360)/linearlow density polyethylene (LLDPE 118W)/120phr magnesium hydroxide(MAGNIFIN A Grades H10A) formulations as a function of CNT 50 or carbonblack content.

DETAILED DESCRIPTION OF THE FIGURES

FIG. 1 shows CNT with different diameter sizes and tube lengths areinvestigated to find compatibility with the other components inthermoplastic clean flame retardant compositions. CM-95 (Hanwhananotech/Korea, multi-walled CNT synthesized by catalytic CVD process,diameter range: 10-15 nm), CNT 50 (NanoKarbon, Korea nano Ind. Co.,multi-walled CNT synthesized by catalytic CVD process, inner diameter:10-30 nm, outer diameter: 40-60 nm, length distribution: under 20 μm)and CNT 75 (NanoKarbon, Korea nano Ind. Co., multi-walled carbonnanotubes synthesized by catalytic CVD process, inner diameter: 30-50nm, outer diameter: 60-80 nm, length distribution: under 20 μm) areinvestigated for finding better compatibility with the other components.

As preliminary test, a comparison between CNT and carbon black inEVA/MAGNIFIN A Grades H10A formulations is conducted as shown in FIGS.2, 3 and 4. Elongation at break (%) of EVA/120phr H10A formulations as afunction of CNT or carbon black content is shown in FIG. 2. Apparentlydifferent trends are observed from different CNTs even the content isquite small. At the range of up to 4phr content, elongation at breakdecreases with increase of CNT content. CM-95 shows the lowestelongation at break even compared to carbon black. It is considered thatthe mechanical properties depend on the size of particle. When onlyCNT50/CNT75 formulations and CB contained formulations are compared inelongation at break, it is apparent that CNT50/CNT75 formulations showhigher values than CB contained formulations. From the results, it isconsidered that CNT50/CNT75 can be used in HFFR formulations instead ofCB for obtaining higher elongation at break values.

Tensile strength of EVA/120phr H10A formulations as a function of CNT orCB content is shown in FIG. 3. Apparently different trends are observedfrom different CNTs even at small contents. At the range of up to 6phrcontent, tensile strength increases with increase of CNT content. CM-95shows the highest tensile strength even compared to CB containedformulations. It is proposed that smaller size of particles shows highertensile strength, therefore, CM-95 shows the highest tensile strengthand CB shows the lowest tensile strength. When only CNT50/CNT75formulations and CB contained formulation are compared in terms oftensile strength, it is found that CNT50/CNT75 formulations show muchhigher values than CB contained formulations.

From the results of FIGS. 2 and 3, it is apparent that CNT50/CNT75formulations show higher values than CB contained formulations in bothmechanical properties (elongation at break and tensile strength).Therefore, it is considered that CNT50/CNT75 can be used in HFFRformulations instead of CB for obtaining higher mechanical properties(elongation at break and tensile strength).

LOI (%) of EVA/120phr H10A formulations as a function of CNT or CBcontent is shown in FIG. 4. CNT50/CNT75 and carbon black formulationsshow almost similar flame retardancy. Flame retardancy increases withincrease of content in CNT50, CNT75 and CB contained formulations.

From the results of FIGS. 2, 3 and 4, it is apparent that CNT50/CNT75formulations show higher mechanical properties without losing flameretardancy compared with CB contained formulations. Therefore,CNT50/CNT75 can be used in HFFR formulations instead of CB for obtaininghigher mechanical properties (elongation at break and tensile strength)and flame retardancy.

For reconfirming the results of FIGS. 2, 3 and 4, the relationshipsbetween CNT50 and CB in EVA/LLDPE/MAGNIFIN A Grades H10A areinvestigated as shown in FIGS. 5, 6 and 7. LLDPE (20% weight content) ismixed with EVA to increase thermal properties. Elongation at break (%)of Evaflex 360/LLDPE 118W/120phr H10A formulations as a function of CNT50 or CB is shown in FIG. 5. It is apparently observed that CNT50contained formulations show higher elongation at break values comparedwith CB contained formulations. Elongation at break slightly increaseswith increase of CNT50 content while elongation at break slightlydecreases with increase of CB content.

Tensile strength of Evaflex 360/LLDPE 118W/120phr H10A formulations as afunction of CNT50 or CB content is shown in FIG. 6. It is apparentlyobserved that CNT50 contained formulations show higher tensile strengthvalues compared with CB contained formulations. Tensile strengthincreases with increase of CNT50 or CB. However, rate of increase ofCNT50 contained formulations is higher than that of CB containedformulations. For both mechanical properties, higher values are obtainedby CNT50 compared with CB.

LOI (%) of Evaflex 360/LLDPE 118W/120phr H10A formulations as a functionof CNT or CB content is shown in FIG. 4. Higher flame retardancy isobserved by CNT50 contained formulations compared with CB containedformulations. Flame retardancy increases with increase of CNT50 or CBcontent. However, the rate of increase for CNT50 contained formulationsis higher than that of CB contained formulations. The highest LOI isobserved at 4phr CNT50 contained formulations.

DETAILED DESCRIPTION

There are two types of clean flame retardant materials for wire andcable, i.e., thermoplastic (without cross-linking) and thermosetting(cross-linked). This invention relates to thermoplastic type clean flameretardant material for wire and cable. More particularly, this inventionrelates to black color thermoplastic clean flame retardant compositionsfor improving mechanical properties and flame retardancy. The inventedclean flame retardant compositions may be particularly suitable for usein enhanced cable insulations meeting IEC 60502, BS 6724 and BS 7655standards for thermoplastic compounds requirements.

This invention pertains to unique formulation and processing method ofclean flame retardant material for wire and cable. The present inventionmay lead to improved mechanical properties, particularly tensilestrength and elongation break without deteriorating flame retardancy.

Clean flame retardant compositions consist of 100 parts polymer (EVA(Ethylene Vinyl Acetate), EVA/polyethylene, EEA (Ethylene EthylAcrylate)/polyethylene or Ethylene Alpha Olefin/polyethylene) by weightand 100-150 parts inorganic flame retardant such as magnesium hydroxide,aluminum hydroxide and huntite hydromagnesite by weight, 2-20 partsintumescent flame retardant such as red phosphorus, zinc borate, andboric acid by weight, 0.5-1.5 parts antioxidant by weight. Based onparticular application, additional coloring agent, weathering protectionagent, processing aid, coupling agent, lubricant and thermal stabilizermay be added to the composition.

The polymer may be (by weight) under 50% of total compound in a cleanflame retardant composition. In addition, the particle size of mostflame retardants which are used in clean flame retardant compositionsmay be under 50 μm. The aforementioned particle size of the flameretardant exhibits better dispersion properties to obtain bettermechanical properties. When the polymer and the flame retardants aremixed well in the compounding process results in a balanced arrangementof polymer and flame retardant to obtain better mechanical properties.

This invention pertains to special formulations with unique materials ofclean flame retardant materials for wire and cable. The presentinvention leads to improved flame retardancy and mechanical properties,particularly maintaining elongation at break/tensile strength withoutdeteriorating flame retardancy in black color thermoplastic type cleanflame retardant compositions.

More particularly, this invention relates to formulations of black colorthermoplastic clean flame retardant compositions which do not containcarbon black. As shown in Conventional examples, it is known that carbonblack can increase flame retardancy however it may decreased mechanicalproperties specially elongation break in black color thermoplastic cleanflame retardant compositions compared to the present invention. Thecurrent composition may pass V-0 of UL 94 test with satisfactorymechanical properties of minimum tensile strength 8.8 MPa and minimumelongation at break 125% based on IEC 60502 standards compared toConventional examples.

Moreover, in most commercial situations, mechanical properties arealways fluctuating after production of wire and cable. The extrudingtemperature can be changed by seasonal environmental conditions, speedand cable size are also changed by various specifications and client'sdemand. Therefore, mechanical properties of clean flame retardantcompositions should show at least 20-30% higher than normalspecification values. When the mechanical properties just meet thespecification values, the quality control margin is very tight,accordingly, some products may fail specifications.

The main points for selecting the new material in this invention are asfollows:

-   -   The new material which can be used instead of carbon black to        increase flame retardancy in thermoplastic clean flame retardant        compositions.    -   This material may exhibit an increase in mechanical properties,        specially, elongation at break.    -   This material must be compatible with the other flame retardant        composition components.

Carbon nano tubes (CNT) is very compatible for this purpose. Other flamereartdant compositions that are compatible with CNT are magnesiumhydroxide, huntite hydromagnesite, aluminum hydroxide, zinc borate,carbon black and etc. These components have very fine structure and areuseful in flame retardant composition.

CNT is considered as allotrope of carbon with nanostructure whoselength-to-diameter ratio is very long. These cylindrical carbonmolecules have novel properties which make them potentially useful inmany applications. It is suggested that allotropes may contribute toincrease in flame retardancy in clean flame retardant compositions;nevertheless, mechanical properties of compositions are not deterioratedbecause CNT is constructed by nanostructure. This is the main reason touse CNT instead of carbon black in clean flame retardant composition inthe current invention.

Several different types of CNT are investigated to find bestcompatibility with the other components in thermoplastic clean flameretardant compositions. CNT is categorized as single walled nanotube(SWNT), multi-walled nanotube (MWNT), fullerene structural, sphericalbuckyball type structural, different diameter sizes and tube lengths. Inthis invention, three multi-walled CNTs with different diameter sizesand tube lengths are investigated to find compatibility with the othercomponents in thermoplastic clean flame retardant compositions. CM-95(Hanwha nanotech/Korea, multi-walled CNT synthesized by catalytic CVDprocess, diameter range: 10-15 nm), CNT 50 (NanoKarbon, Korea nano Ind.Co., multi-walled CNT synthesized by catalytic CVD process, innerdiameter: 10-30 nm, outer diameter: 40-60 nm, length distribution: under20 μm) and CNT 75 (NanoKarbon, Korea nano Ind. Co., multi-walled carbonnanotubes synthesized by catalytic CVD process, inner diameter: 30-50nm, outer diameter 60-80 nm, length distribution: under 20 μm) areinvestigated for finding better compatibility with the other components.

The following are an example of Conventional formulations that showresults of clean flame retardant compositions in terms of mechanicalproperties and flame retardancy.

As shown in examples, three different types of flame retardants areinvestigated, such as MAGNIFIN A Grades H10A (magnesium hydroxide,formula: Mg(OH)₂ producer: Albemarle/France), Ultracarb LH 15×(huntitehydromagnesite, formula: Mg₃ Ca(CO₃)₄, Mg₅(CO₃)₄(OH)₂3H₂O, producer:Minelco/USA) and KISUMA 5B (magnesium hydroxide, formula: Mg(OH)₂,Producer: Kyowa Chemical/Japan). Evaflex 360 (ethylene vinyl acetate,producer: DuPont-Mitsui Polychemicals Co./Japan, vinyl acetate content:25%, melt mass-flow rate (MFR) (190° C./2.16 kg): 2.0 g/10 min) andLLDPE 118 (melt flow index: 1.0 g/10 min, producer: SABIC/Saudi Arabia)are used as base polymers. Irganox 1010 (chemical name: pentaerythritoltetrakis(3(3,5-di tert-buty-4-hydroxyphenyl)propionate, CIBA specialtychemicals/Switzerland, melting range 110-125° C.) is used asantioxidant. Corax N550 (producer: Degussa, Germany, semi-active carbonblack with high structure, ash content: 0.5%) is used as carbon black.All materials of experimental are summarized in Table 1.

TABLE 1 Materials list. Function/Chemical Name Material ProducerCharacteristics Polymer, ethylene vinyl Evaflex 360 DuPont-Mitsui vinylacetate acetate (EVA) Polychemicals Co./Japan content: 25%, meltmass-flow rate (MFR) (190° C./2.16 kg): 2.0 g/10 min) Polymer, linearlow LLDPE 118 SABIC/Saudi Arabia melt flow index: 1.0 g/ densitypolyethylene 10 min (LLDPE) Flame retardant, MAGNIFIN A Albemarle/Francemagnesium hydroxide, Grades H10A formula: Mg(OH)₂ Flame retardant,huntite Ultracarb LH Minelco/USA hydromagnesite, 15X formula:Mg₃Ca(CO₃)₄, Mg₅(CO₃)₄(OH)₂3H₂O Flame retardant, KISUMA 5B KyowaChemical/Japan magnesium hydroxide, formula: Mg(OH)₂ Antioxidant,Irganox 1010 CIBA specialty melting range: 110-125° C. pentaerythritolchemicals/Switzerland tetrakis(3(3,5-di tert-buty- 4-hydroxyphenyl)propionate, Carbon black Corax N550 Degussa/Germanysemi-active carbon black with high structure, ash content: 0.5%Intumescent flame Exolit RP 692 Clariant/France phosphorus content:retardants, red approx. 50% (w/w) phosphorus masterbatch Intumescentflame Firebrake ZB Borax/USA retardants, zinc borate Intumescent flameBoric Acid Rose Mill Chemicals & retardants, Boric Acid Lubricant/USACarbon nano tube CM-95 Hanwha nanotech/Korea multi-walled CNTsynthesized by catalytic CVD process, diameter ranges: 10-15 nm Carbonnano tube CNT 50 NanoKarbon, Korea nano multi-walled CNT Ind. Co.synthesized by catalytic CVD process, inner diameter: 10-30 nm, outerdiameter: 40-60 nm, length distribution: under 20 μm Carbon nano tubeCNT 75 NanoKarbon, Korea nano multi-walled CNT Ind. Co. synthesized bycatalytic CVD process, inner diameter: 30-50 nm, outer diameter: 60-80nm, length distribution: under 20 μm

The reason for using LDPE (or LLDPE) in base polymers is to increasethermal properties of thermoplastic clean flame retardant compositions.In general, high filler mixable polymers, such as ethylene vinyl acetate(EVA), ethylene ethyl acrylate (EEA) or ethylene alpha olefin have verylow softening temperatures. Mostly, their softening points are under100° C. Therefore, it is apparent that using only low softeningtemperature grade polymers without any high temperature grade polymersin base polymers will lead to loss in thermal properties. The thermalaging test condition of thermoplastic clean flame retardant material is100° C. for 136 hours. To achieve appropriate thermal stability, themixing of high temperature grade polymer such as polyethylene isrequired. Therefore, the base polymers in thermoplastic clean flameretardant compositions should have appropriate thermal stability to passthe thermal aging test (at 100° C. for 136 hours). However, polyethylenehas low filler mix ability and lower flame retardancy, accordingly,ethylene vinyl acetate/polyethylene compounded base polymers can mixless volume of flame retardants and decrease flame retardancy comparedto 100% ethylene vinyl acetate base polymer.

Mechanical properties (tensile strength and elongation at break) weremeasured using a universal testing machine Model 5543 from Instron, USAin accordance with ASTM D 638M with testing conditions: speed of 500mm/minute at 25° C. LOI (Limiting Oxygen Index) is a simple method toevaluate the flame retardancy of the materials. LOI was performed usingan apparatus of Fire Testing Technology limited (Incorporating StantonRedcroft), UK in accordance with ISO 4589 and ASTM D 2863. LOIcorresponds to the minimum percentage of oxygen needed for thecombustion of specimens (80×10×1 mm) in an oxygen-nitrogen atmosphere.The other method to estimate the flame retardancy of the materials is UL94 Flammability standard by Underwriters Laboratories, USA. UL 94 testwas performed using a flammability chamber of CEAST Co., Italy, inaccordance with ASTM D 635 for horizontal and ASTM D 3801 for verticaltest positions. The standard classifies plastics according to how theyburn in various orientations and thicknesses. From lowest (leastflame-retardant) to highest (most flame-retardant), the classificationsare shown in Table 2:

TABLE 2 Standard Classification of material based on their orientationand thickness Standard Conditions Classification Description allowed HBSlow burning on a horizontal specimen; burning rate <76 mm/min forthickness <3 mm V2 Burning stops within 30 seconds Drips of flaming on avertical specimen particles are allowed V1 Burning stops within 30seconds No drips allowed on a vertical specimen V0 Burning stops within10 seconds No drips allowed on a vertical specimen

Conventional Example 1

Content/Property C-1 C-2 C-3 C-4 C-5 Ethylene vinyl acetate 80 80 80 8080 (Evaflex 360) Linear low density 20 20 20 20 20 polyethylene (LLDPE118W) Magnesium hydroxide 120 120 120 120 120 (MAGNIFIN A Grades H10A)Carbon black (Corax 0 2 4 6 8 N550) Pentaerythritol 1 1 1 1 1tetrakis(3(3,5-di tert- buty-4- hydroxyphenyl)propionate (Irganox1010)Tensile strength (MPa) 9 9 9.5 9.5 10 Elongation at break (%) 165 150150 150 145 LOI (%) 31 33 34 37 39 UL 94 test H-B H-B H-B H-B H-B

These formulations are basic thermoplastic clean flame retardantcompositions which consist of one main flame retardant (magnesiumhydroxide (MAGNIFIN A Grades H10A)) with various contents of carbonblack (Corax N550). From the experimental results, it is found thatelongation at break decreases slightly even though tensile strength andflame retardancy increase with increase of carbon black (Corax N550)content.

Conventional Example 2

Content/Property C-6 C-7 C-8 C-9 C-10 Ethylene vinyl acetate 80 80 80 8080 (Evaflex 360) Linear low density 20 20 20 20 20 polyethylene (LLDPE118W) Huntite hydromagnesite 120 120 120 120 120 (Ultracarb LH 15X)Carbon black (Corax 0 2 4 6 8 N550) Pentaerythritol 1 1 1 1 1tetrakis(3(3,5-di tert- buty-4- hydroxyphenyl)propionate (Irganox1010)Tensile strength (MPa) 7 7 8 9 9 Elongation at break (%) 160 145 140 130130 LOI (%) 27 32 34 35 37 UL 94 test H-B H-B H-B H-B H-B

Similar to Conventional Example 1, these formulations are also basicthermoplastic clean flame retardant compositions with various contentsof carbon black (Corax N550), and the main flame retardant is changedfrom magnesium hydroxide (MAGNIFIN A Grades H10A) to huntitehydromagnesite (Ultracarb LH 15×). From the experimental results,similar tendency is observed, i.e. it is found that elongation at breakdecreases slightly even though tensile strength and flame retardancyincrease with increase of carbon black (Corax N550) content.

Conventional Example 3

Content/Property C-11 C-12 C-13 C-14 C-15 Ethylene vinyl acetate 80 8080 80 80 (Evaflex 360) Linear low density 20 20 20 20 20 polyethylene(LLDPE 118W) Magnesium hydroxide 120 120 120 120 120 (KISUMA 5B) Carbonblack (Corax 0 2 4 6 8 N550) Pentaerythritol 1 1 1 1 1 tetrakis(3(3,5-ditert- buty-4- hydroxyphenyl)propionate (Irganox1010) Tensile strength(MPa) 10 9.5 9.5 9.5 9.5 Elongation at break (%) 550 500 480 450 420 LOI(%) 27 31 32 32 35 UL 94 test H-B H-B H-B H-B H-B

As shown in Conventional example 3, not much change in tensile strengthis observed with increase of carbon black content. On the contrary,influence of carbon black on elongation at break is quite prominent.Elongation at break decreases with increase of carbon content. Normally,increase of filler content may cause decrease in mechanical properties.Carbon black plays the role of filler in compounds; however under 8phrof carbon black content by weight, the tensile strength remains almostconstant while elongation at break is greatly influenced. In addition,it is apparent that LOI (%) increases with increase of carbon blackcontent. From our experimental, it is definite that carbon blackincreases flame retardancy and decreases elongation at break in blackcolor thermoplastic clean flame retardant compositions.

In Conventional examples 1, 2 and 3, no composition passes V-0 of UL 94test with satisfactory mechanical properties of minimum tensile strength8.8 MPa and minimum elongation at break 125% based on IEC 60502standards. To pass V-0 of UL 94 test, higher than 120phr content of mainflame retardant with secondary (intumescent) flame retardants such asred phosphorus, zinc borate, and (or) boric acid has to be compounded.However, additional main and intumescent flame retardants can causedeterioration of mechanical properties in spite of improvement in flameretardancy as shown in Conventional example 4. Exolit RP 692 (redphosphorus master batch, producer: Clariant/France, phosphorus content:approx. 50% (w/w)), Firebrake ZB (zinc borate, producer: Borax/USA) andBoric Acid (Producer: Rose Mill Chemicals & Lubricant/USA) are used asintumescent flame retardants. Formulations of C-17 to C-20 which containcarbon black show big drop in elongation at break in spite of high LOIvalues. Many scientists are eager to find a substitute material forcarbon black, which does not deteriorate mechanical properties withimproved flame retardancy in thermoplastic clean flame retardantcompositions. In our invention, new material which can substitute carbonblack in thermoplastic clean flame retardant compositions for thisparticular purpose is introduced.

Conventional Example 4

Content/Property C-16 C-17 C-18 C-19 C-20 Ethylene vinyl acetate 80 8080 80 80 (Evaflex 360) Linear low density 20 20 20 20 20 polyethylene(LLDPE 118W) Magnesium hydroxide 130 130 130 130 130 (MAGNIFIN A GradesH10A) Red Phosphorus 5 5 5 5 5 (RP-692) Zinc Borate 5 5 5 5 5 (FirebrakeZB) Boric Acid 2 2 2 2 2 Carbon black (Corax N550) 0 2 4 6 8Pentaerythritol tetrakis(3(3,5- 1 1 1 1 1 di tert-buty-4-hydroxyphenyl)propionate (Irganox1010) Tensile strength (MPa) 10 9.5 1010 10 Elongation at break (%) 150 130 115 105 100 LOI (%) 34 35 37 38 40UL 94 test V-0 V-0 V-0 V-0 V-0

In the current invention, clean flame retardant compositions consist of100 parts polymer (EVA (Ethylene Vinyl Acetate), EVA/polyethylene, EEA(Ethylene Ethyl Acrylate)/polyethylene or Ethylene AlphaOlefin/polyethylene) by weight and 100-150 parts inorganic flameretardants such as magnesium hydroxide, aluminum hydroxide and huntitehydromagnesite by weight, 2-20 parts intumescent flame retardants suchas red phosphorus, zinc borate, and boric acid by weight, 0.5-1.5 partsantioxidants by weight. Based on particular application, additionalcoloring agent, weathering protection agent, processing aid, couplingagent, lubricant and thermal stabilizer are added to the compositions.

In the current invention the polymer portion (by weight) is under 50%total compound in clean flame retardant compositions. In addition, theparticle size of most flame retardants which are used in clean flameretardant compositions are under 50 μm. Excellent dispersion ofpolymer/flame retardants is very important to obtain better mechanicalproperties. When polymer/flame retardants are well mixed in compoundingprocess, it is assumed that the arrangement of polymer and flameretardants is very well balanced. The invention specially takes severalaspects of improvements into consideration, such as improving mechanicalproperty and arrangement of polymers containing flame retardants in ahighly filled composition.

The current invention pertains to special formulations with uniquematerials of clean flame retardant materials for wire and cable. Thepresent invention leads to improved flame retardancy and mechanicalproperties, particularly maintaining elongation at break/tensilestrength without deteriorating flame retardancy in black colorthermoplastic type clean flame retardant compositions.

More particularly, this invention relates to formulations of black colorthermoplastic clean flame retardant compositions which do not containcarbon black which is generally used in ordinary black color clean flameretardant compositions at present. As shown in Conventional example 1,2, and 3, it is known that carbon black can increase flame retardancyhowever it deteriorates mechanical properties specially elongation atbreak in black color thermoplastic clean flame retardant compositions.Therefore, it is very difficult to obtain satisfactory compositionswhich meet both main property standards such as flame retardancy andmechanical properties. It is hard to obtain suitable formulations whichpass V-0 of UL 94 test with satisfactory mechanical properties ofminimum tensile strength 8.8 MPa and minimum elongation at break 125%based on IEC 60502 standards in Conventional examples 1, 2 and 3.

Moreover, in most commercial situations, mechanical properties arealways fluctuating after production of wire and cable. The extrudingtemperature, speed and cable size varies depending on environmentalconditions, client requirements and standard specifications. Therefore,mechanical properties of clean flame retardant compositions should showat least 20-30% higher than normal specification values in order to passthe stringent quality control tests.

In our invention, for solving deterioration of mechanical propertieswhile maintaining high flame retardancy in black color thermoplasticclean flame retardant compositions, new material is introduced insteadof carbon black.

As shown in FIG. 1, it is observed that CM-95 has much smaller diametersize and much higher length-to-diameter ratio compared to CNT 50 and CNT75.

As preliminary test, the relationships between MAGNIFIN A Grades H10Aand CNT/carbon black are investigated as shown in pre-test examples. Inpre-test examples, only Evaflex 360 is used as base matrix polymer. Therelationships between elongation at break/CNT (or carbon black content),tensile strength/CNT (or carbon black content) and flame retardancy/CNT(or carbon black content) are shown in FIGS. 2-4.

Pre-Test Example 1

Content/Property P-1 P-2 P-3 P-4 Ethylene vinyl acetate 100 100 100 100(Evaflex 360) Magnesium hydroxide 120 120 120 120 (MAGNIFIN A GradesH10A) Carbon black (Corax N550) 0 2 4 6 Pentaerythritol tetrakis(3(3,5-1 1 1 1 di tert-buty-4- hydroxyphenyl)propionate (Irganox1010) Tensilestrength (MPa) 10 9.3 9.5 10.8 Elongation at break (%) 200 175 150 180LOI (%) 33 35 36.5 39

Pre-Test Example 2

Content/Property P-5 P-6 P-7 P-8 Ethylene vinyl acetate 100 100 100 100(Evaflex 360) Magnesium hydroxide 120 120 120 120 (MAGNIFIN A GradesH10A) CM-95 0 2 4 6 (Outer D. = 10-15 nm) Irganox 1010 1 1 1 1 Tensilestrength (MPa) 10.3 11.6 12.0 12.7 Elongation at break (%) 200 165 133135 LOI (%) 33 31.5 31.5 31.5

Pre-Test Example 3

Content/Property P-9 P-10 P-11 P-12 Ethylene vinyl acetate (Evaflex 360)100 100 100 100 Magnesium hydroxide 120 120 120 120 (MAGNIFIN A GradesH10A) Carbon nano tube (CNT50) 0 2 4 6 (Outer D = 40-60 nm)Pentaerythritol tetrakis(3(3,5-di 1 1 1 1 tert-buty-4-hydroxyphenyl)propionate (Irganox1010) Tensile strength (MPa) 10.3 11.311.5 12.0 Elongation at break (%) 200 200 180 185 LOI (%) 33 34.5 36.540.5

Pre-Test Example 4

Content/Property P-13 P-14 P-15 P-16 Ethylene vinyl acetate 100 100 100100 (Evaflex 360) Magnesium hydroxide 120 120 120 120 (MAGNIFIN A GradesH10A) Carbon nano tube 0 2 4 6 (CNT75) (Outer D. = 60-80 nm)Pentaerythritol 1 1 1 1 tetrakis(3(3,5-di tert-buty- 4-hydroxyphenyl)propionate (Irganox1010) Tensile strength (MPa) 10.3 10.710.3 11.8 Elongation at break (%) 200 190 165 190 LOI (%) 33 35.5 36.540

Elongation at break and tensile strength of EVA/120phr H10A formulationsas a function of CNT or carbon black content are shown in FIGS. 2 and 3.Surprisingly, different trends are demonstrated by different CNTs eventhough the content is the same and is quite small. At the range of up to4phr content, elongation at break decreases and tensile strengthincreases with increase of CNT content. It is interesting to notice thatCM-95 contained formulations show the lowest elongation at break and thehighest tensile strength among all investigated formulations includingcarbon black contained formulations. It is observed that smallerparticle size shows higher tensile strength, therefore, CM-95 shows thehighest tensile strength and carbon black shows the lowest tensilestrength. It is considered that mechanical properties depend mainly uponthe size of particles.

As shown in FIG. 4, CNT50, CNT75 and carbon black formulations showalmost similar trends of flame retardancy as a function of content, onthe contrary, CM-95 formulation shows very low flame retardancy. Flameretardancy increases with increase of content in CNT50, CNT75 and carbonblack formulations. Flame retardancy increases with as low as 2phr ofCNT50, CNT75 or carbon black by weight. It is observed that thesematerials have strong influence on flame retardancy in combination withmagnesium hydroxide (MAGNIFIN A Grades H10A) except in the case ofCM-95. It is considered that the size of diameter and the length of tubeinfluence mechanical properties and flame retardancy. Namely, CM-95 hastoo small diameter with too long length which leads to poorcompatibility with the other components, consequently CM-95 formulationsshow poor results of mechanical properties and flame retardancy.

From the results of mechanical properties and flame retardancy, CNT50contained formulations show the best results in both properties. Whenonly CNT50 formulations and carbon black formulations are compared interms of mechanical properties (i.e. elongation at break and tensilestrength), it is apparent that CNT50 contained formulations show muchhigher properties than carbon black formulations. Accordingly, it isconsidered that CNT50 has proper size and length for use in clean flameretardant compositions. Namely, CNT of outer diameter of 40-60 nm andlength distribution of under 20 μm can be used in thermoplastic cleanflame retardant compositions instead of carbon black to increasemechanical properties and flame retardancy. Therefore, CNT 50 isselected for detailed comparative investigation with carbon black.

The following non-limiting examples illustrate formulations of theinvented compositions.

Example 1

Content/Property 1 2 3 4 Ethylene vinyl acetate 80 80 80 80 (Evaflex360) Linear low density 20 20 20 20 polyethylene (LLDPE 118W) Magnesiumhydroxide 120 120 120 120 (MAGNIFIN A Grades H10A) Carbon black — — — —(Corax N550) Carbon nano tube 0 2 4 6 (CNT50) (Outer D = 40-60 nm)Pentaerythritol tetrakis 1 1 1 1 (3(3,5-ditert-buty-4- hydroxyphenyl)propionate (Irganox1010) Tensile strength (MPa) 12 13 14 14 Elongationat break (%) 180 175 170 170 Thermal Retention of Over 80% aging tensileat 100° C. strength for (%) 168 hrs Retention of Over 80% elongation atbreak (%) LOI (%) 34 38 39 39 UL 94 test H-B H-B H-B V-2 Volumeresistivity(Ωcm) 4 × 10¹⁵ 2 × 10¹⁵ 2 × 10¹⁵ 1 × 10¹⁵

Volume resistivity is measured at room temperature (25° C.) inaccordance with ASTM D257 using high resistance meter of Model HP4339B,HP, USA. From the results, it is observed that even the highest CNT50content (6phr (per hundred resin)) by weight formulation (run No. 4)shows very high volume resistivity (Ω·cm). Therefore, it is apparentthat CNT50 contained formulations that are suitable to be used in cableinsulation materials.

As shown in FIGS. 5 and 6, it is observed that CNT50 formulations showhigher mechanical properties compared to carbon black formulations.Elongation at break slightly increases with increase of CNT50 contentwhile elongation at break slightly decreases with increase of carbonblack content. In addition, tensile strength increases with increase ofCNT50 or carbon black, however the rate of increase for CNT50 content ishigher than that of carbon black content. Namely, higher values areobtained by CNT50 compared to carbon black for both mechanicalproperties. These results show that CNT50 may be very suitable flameretardant in thermoplastic clean flame retardant compositions if thesame or higher flame retardancy is achieved with CNT50.

As shown in FIG. 7, surprisingly, higher flame retardancy is observed byCNT50 formulations compared to carbon black formulations. Flameretardancy increases with increase of CNT50 or carbon black content.However, the rate of increase for CNT50 formulations is higher than thatof carbon black formulations.

In addition, volume resistivity (Ω·cm) of CNT 50 and carbon blackformulations is over 1×10¹⁵Ω·cm which is sufficient for use in wire andcable insulation and jacket materials.

From the overall results of mechanical properties, flame retardancy andelectrical properties for CNT 50/carbon black formulations, CNT50 isreally a suitable material which can be used instead of carbon black inthermoplastic clean flame retardant compositions.

The main key points of this invention are re-confirmed from aboveexperimental. Namely, CNT of outer diameter of 40-60 nm and lengthdistribution of under 20 μm can be used in thermoplastic clean flameretardant compositions instead of carbon black to improve mechanicalproperties and flame retardancy.

The compounding of above compositions is preferably conducted asfollows, namely, EVA and LDPE are melted and mixed in internal mixer forfour minutes at 150° C. Then, rest of additives and flame retardants aremixed with already melted polymers for 10 minutes at 150° C. Thepre-mixed compounds are moved to two roll mill/guider cutter/pelletizingextruder and then pelletized. At this step, temperature of two rollmixer is kept around 150° C. and mixture is processed for 5-10 minutes.

Another important processing parameter for clean flame retardantmaterials compared to routine thermoplastics is that the extrudingtemperature of clean flame retardant materials is 160° C.-200° C. whilethat of routine thermoplastics is 200-250° C. The extruding temperatureof clean flame retardant materials is lower than routine thermoplasticssuch as polyethylene because clean flame retardant materials are mainlyconsisted of low softening temperature grade polymers such as EVA(Ethylene Vinyl Acetate), Ethylene Alpha Olefin or Ethylene EthylAcrylate.

Sheets of test specimen for mechanical properties and flame retardancyare prepared by hot press and compressed at 180° C. for 10 minutes withthickness of 2 mm Likewise, the above materials are preferably extrudedat temperature 160° C.-200° C. onto conductors to prepare the insulatedcable and check process ability. This extruding process is exactly thesame as routine thermoplastic method. During cable extrusion of abovecompositions, non CNT 50 content composition (run number 1) and 2-4parts CNT 50 per hundred resin by weight (run numbers 2 and 3) show thebest process ability and excellent surface smoothness of finishedcables.

Similar to Example 1, ethylene vinyl acetate (Evaflex 360)/magnesiumhydroxide (KISUMA 5B) (120phr)/CNT 50 formulations are conducted. Thedetailed examples of formulations are shown in EXAMPLE 2. As shown inresults for ethylene vinyl acetate (Evaflex 360)/magnesium hydroxide(MAGNIFIN A Grades H10A) (120phr) formulations, 2-4 parts CNT 50 perhundred resin by weight show the best performance. Non CNT 50 contentcomposition (run number 5) and 2-4 parts CNT 50 per hundred resin byweight (run numbers 6 and 7) show the best process ability and excellentsurface smoothness of finished cables.

Example 2

Content/Property 5 6 7 8 Ethylene vinyl acetate 80 80 80 80 (Evaflex360) Linear low density 20 20 20 20 polyethylene (LLDPE 118W) Magnesiumhydroxide 120 120 120 120 (KISUMA 5B) Carbon nano tube 0 2 4 6 (CNT50)(Outer D = 40-60 nm) Pentaerythritol tetrakis 1 1 1 1 (3(3,5-di tert-buty-4-hydroxyphenyl) propionate (Irganox1010) Room Tensile 10 10 10 10temperature strength (MPa) Elongation 550 500 450 440 at break (%)Thermal Retention Over 80% aging at of tensile 100° C. for strength 168hrs (%) Retention Over 80% of elongation at break (%) LOI (%) 27 30 3335 UL 94 test H-B H-B H-B V-2 Volume resistivity(Ωcm) 3 × 10¹⁵ 3 × 10¹⁵1 × 10¹⁵ 1 × 10¹⁵

To increase flame retardancy and achieve V-0 of UL94 test, intumescentflame retardants such as Exolit RP 692 (red phosphorus masterbatch,producer: Clariant/France, phosphorus content: approx. 50% (w/w)),Firebrake ZB (zinc borate, producer: Borax/USA) and Boric Acid(Producer: Rose Mill Chemicals & Lubricant/USA) are used in ethylenevinyl acetate (Evaflex 360)/magnesium hydroxide (MAGNIFIN A Grades H10A)(120phr) formulations as shown in EXAMPLE 3. Processing of test specimenand cable extrusion is the same as previous methods.

From the results, it is found that 2-4 parts CNT 50 per hundred resin byweight (run numbers 10 and 11) compositions show excellent mechanicalproperties and flame retardancy. Specially, all compositions meet V-0 ofUL94 test and volume resistivity (Ω·cm) is sufficient for use in wireand cable insulation materials. Elongation at break of run numbers 10and 11 decreases slightly at CNT 50 content of 2-4 parts per hundredresin by weight. If carbon black is used in run numbers 10 and 11instead of CNT 50, elongation at break is greatly decreased as shown inConventional EXAMPLE 3. In addition, all compositions show excellentthermal properties by passing thermal aging test (100° C.×136 hrs).

Non CNT 50 content composition (run number 9) and 2-4 parts CNT 50 perhundred resin by weight (run numbers 10 and 11) compositions show thebest process ability and excellent surface smoothness for finishedcables.

Example 3

Content/Property 9 10 11 12 Ethylene vinyl acetate 80 80 80 80 (Evaflex360) Linear low density 20 20 20 20 polyethylene (LLDPE 118W) Magnesiumhydroxide 130 130 130 130 (MAGNIFIN A Grades H10A) Red phosphorus 5 5 55 (RP-692) Zinc borate 5 5 5 5 (Firebrake ZB) Boric acid 2 2 2 2 Carbonnano tube 0 2 4 6 (CNT50) (Outer D = 40-60 nm) Pentaerythritol tetrakis1 1 1 1 (3(3,5-di tert-buty-4- hydroxyphenyl) propionate (Irganox1010)Room Tensile 10 11 11 11.5 temperature strength (MPa) Elongation 150 145145 140 at break (%) Thermal Retention Over 80% aging at of tensile 100°C. for strength 168 hrs (%) Retention Over 80% of elongation at break(%) LOI (%) 34 36 38 39 UL 94 test V-0 V-0 V-0 V-0 Volumeresistivity(Ωcm) 2 × 10¹⁵ 1 × 10¹⁵ 2 × 10¹⁵ 9 × 10¹⁴

Although the present embodiments have been described with reference tospecific example embodiments, it will be evident that variousmodifications and changes may be made to these embodiments withoutdeparting from the broader spirit and scope of the various embodiments.Accordingly, the specification and examples are to be regarded in andescriptive rather than a restrictive sense.

What is claimed is:
 1. A method of mixing a thermoplastic composition,comprising: melting a composition for 10 minutes at 150° C. comprising:a polymer 100 parts by weight; and a polyethylene polymer 20 parts byweight.
 2. A method according to claim 1, further comprising: adding thefollowing to the composition as a mixture, an inorganic flame retardant50-250 parts by weight; an intumescent flame retardant 0-100 parts byweight; an antioxidant 0.1-1.5 parts by weight; a processing aid 1-10parts; a carbon nano tube 1-6 parts by weight; and mixing for 10 minutesat 150° C.
 3. A method according to claim 2 further comprising adding2-6 parts by weight of the carbon nano tube.
 4. A method of claim 2further comprising: extruding the thermoplastic extrudable compositionwithout post curing.
 5. A method of claim 4 further comprising:maintaining an extruding temperature between 160°-200° C.